CN1258713A - Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage - Google Patents

Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage Download PDF

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Publication number
CN1258713A
CN1258713A CN98122187.4A CN98122187A CN1258713A CN 1258713 A CN1258713 A CN 1258713A CN 98122187 A CN98122187 A CN 98122187A CN 1258713 A CN1258713 A CN 1258713A
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China
Prior art keywords
catalytic cracking
assistant
transferring assistant
sulfur transferring
sulfur
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Granted
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CN98122187.4A
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Chinese (zh)
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CN1122702C (en
Inventor
王龙延
郭海卿
齐文义
苏淑琴
邓先梁
刘金龙
刘淑芳
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Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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Priority to CN98122187.4A priority Critical patent/CN1122702C/en
Priority to JP5020A priority patent/JP2000204378A/en
Publication of CN1258713A publication Critical patent/CN1258713A/en
Priority to US10/292,681 priority patent/US6790343B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium

Abstract

The assistant is oil soluble or water soluble solution, emulsion or suspension comprising metal compounds, solvent and auxiliary components. The metal compounds are oxide, hydroxide, organic salt, inorganic salt or complex of at least two of alkaline earth metals, transition metals and rare earth metals; the solvent is water, alcohol or hydrocarbon; and the auxiliary components include alcohol, ethers, esters, amines, amides, alcohol amines and ionic or non-ionic surfactant. A water soluble assistant contains metal compounds 30-80 wt%, solvent 10-40 wt% and auxiliary components 10-30 wt%, while an oil soluble assistant contains metal components 50-85 wt%, solvent 10-30 wt%, and auxiliary components 5-20 wt%. The assistant may be injected to reactor solely or together with material to be catalytically cracked or steam, and has a deposited amount in catalyst of 0-3 wt%.

Description

A kind of sulfur transferring assistant for catalytic cracking of hydrocarbon and using method thereof
The present invention relates to sulfur transferring assistant for catalytic cracking of hydrocarbon and using method thereof, especially in the refining of petroleum field, be used for the sulfur transferring assistant and the using method thereof of catalytic cracking of hydrocarbon.
Usually, contain 0.3～3.0% sulphur in the catalytically cracked material, the sulphur about 20～60% after the process cracking in the charging is with H 2The S form enters reacted gas, and 20～70% enter liquid product, and all the other 5～30% enter coke, are deposited on the catalyzer.The H in the reacted gas wherein 2S can be converted into sulphur and reclaim; And the organic sulfide that enters in the light-end products must remove by the hydrofining means.But when the cracking stock sulphur content was higher, light-end products did not often meet quality standard because of sulphur content is higher.Do or take harsher refining means by reducing oil product, can address the above problem, but certainly will make that tooling cost increases, profit reduces; Be deposited on the sulphur in the catalyst coke, in the catalyst regeneration burning process, can be oxidized to SO 2And SO 3(general designation SO x), enter atmosphere with flue gas, cause environmental pollution.SO in the regenerated flue gas in addition xWhen content is higher, also can cause the regenerator device corrosion.
At present, reduce SO in the regeneration fume from catalytic cracking xA kind of widely used technology of sulphur content is to adopt solid-state sulfur transferring assistant in content and the light-end products.Solid-state sulfur transferring assistant can be divided into two classes: a class is for reducing SO in the regenerated flue gas xThe auxiliary agent of concentration; Another kind of is for reducing the particularly auxiliary agent of sulphur content in the gasoline of sulphur content in the light-end products.Wherein U.S. Pat 4,589, and 978 and US5,021,228 disclosed a kind of sulfur transferring assistant belongs to the first kind, Chinese patent CN1,093, the disclosed a kind of sulfur transferring assistant of 735A belongs to second class.In U.S. Pat 4,589, in 978, a kind of solid sulfur transfer catalyst is disclosed, this catalyzer is that 1%～20% lanthanum (La), cerium (Ce) and carrier are formed by content, wherein La:Ce is 1:10～10:1, carrier can be aluminum oxide, silicon oxide, diatomite, zeolite etc., this catalyzer is as particle and catalytic cracking catalyst mix use separately, require catalytic cracking regenerator will reach holomorphosis in the use, excessive 0～2% (volume) of oxygen accounts for 0.5 of system's reserve～8.0% o'clock, SO in add-on xDecreasing ratio can reach 30～80%.At US5, in 021,228, a kind of solid sulfur metastatic composition is disclosed, its composition is: (1) porous alumina carrier; (2) first component actinide metalses are mainly thorium, uranium, and content is 0.5～10% (weight); (3) second component alkaline-earth metal are mainly potassium, sodium, and content is 1～5% (weight), and said composition can be used as the catalytic cracking catalyst component and uses, and can make 60% SO xBe converted into H 2S.At CN1,093, among the 735A, a kind of catalytic cracking catalyst compositions is disclosed, comprise as independent component and be dispersed in the molecular sieve in the inorganic oxide matrix and be the Lewis acid of carrier with the aluminum oxide, its independent component comprises that about 1～50% (weight) is the Ni that is selected from of carrier with the aluminum oxide, Cu, Zn, Cd, Ti, Bi, B, the element of Al etc. and compound, other component of said composition is 5～50% (weight) synthetic faujasites, about 10～60% (weight) clays and 10～30% (weight) are selected from silicon-dioxide, aluminum oxide and silicon-dioxide-aluminum oxide inorganic adhesive, the sulphur content that said composition is observed in the gasoline in the test of riser regenerator medium size installations obviously reduces, and does not reduce gasoline yield simultaneously.In the technology of above-mentioned patent disclosure, the performance of sulfur transferring assistant is single, promptly can only reduce the SO in the regenerated flue gas xConcentration or can only reduce sulphur content in the light-end products, and itself does not have catalytic cracking activity sulfur transferring assistant, and these auxiliary agents join in the system, in fact catalytic cracking catalyst are played diluting effect, make the active reduction of catalyst mixture in the system, the selectivity variation.For example, be 60 equilibrium catalyst for micro-activity (MA), when the sulfur transferring assistant that adds 5%, micro-activity approximately will reduce by 3 units, and its selectivity is wanted obvious variation.On the other hand, existing sulfur transferring assistant all is a solid, requirement has the distribution of particle sizes harmonious with catalytic cracking catalyst, physical strength and sphericity, therefore after this solid particulate adding system, its ratio shared in system's reserve can not be carried out flexible, relatively poor to the device adaptability that sulfur content of raw material often changes, and the processing unit of the strict complexity of needs when preparing this solid particulate.
The object of the present invention is to provide a kind of SO that can reduce simultaneously in the regenerated flue gas xSulphur content in concentration and the light-end products, and,, promptly can only reduce the SO in the regenerated flue gas to improve the single performance of solid sulfur transferring assistant in the prior art to liquid sulfur transferring assistant and using method thereof that activity of such catalysts in the system and selectivity have no adverse effects xConcentration or can only reduce sulphur content in the light-end products, and overcome sulfur transferring assistant to activity of such catalysts and selectivity caused in the system detrimentally affect.
A kind of liquid sulfur transferring assistant provided by the invention, oil soluble or water miscible molecule or colloidal solution, emulsion or the suspension formed by metallic compound, solvent and auxiliary component.Wherein metallic compound is oxide compound, oxyhydroxide, organic acid salt, inorganic acid salt or its complex compound of metal, and described metal is in alkaline-earth metal, transition metal and three groups of metals of rare earth metal two or more, and at least two groups in white these the three groups of metals of its choosing, specifically, can from Mg, Ca, Zn, Ag, Cd, La, Sn, Ce, Ti, Bi, Pb, Al, B, Pr, Ba, Ga, choose metal by described method; The used organic acid of described organic acid salt is selected from one or more in saturated carboxylic acid, unsaturated carboxylic acid, substituted carboxylic acid and the Phenylsulfonic acid, as propionic acid, propanedioic acid, butyric acid, isopropylformic acid, 2-Methyl Butyric Acid, sad, isocaprylic acid, different n-nonanoic acid, phenylformic acid, naphthenic acid, citric acid, tartrate, lipid acid, oleic acid, Witco 1298 Soft Acid, p-methyl benzenesulfonic acid etc.; The used mineral acid of described inorganic acid salt is selected from nitric acid, phosphoric acid, sulfonic acid.Solvent is water, alcohols or hydro carbons, as methyl alcohol, ethanol, benzene,toluene,xylene, ethylbenzene, octane-iso, dodecane, No. 200 solvent wet goods.Auxiliary component is alcohols, ethers, ester class, amine, amides, alcamines or ionic, nonionic surface active agent, as ethylene glycol, glycerol, glycol ether, isopropylcarbinol, methyl tertiary butyl ether, glycol dimethyl ether, propylamine, butylamine, quadrol, 1,4-butanediamine, dimethyl formamide, benzamide, monoethanolamine, diglycolamine, polyvinyl alcohol, hydroxybenzene polyoxydivinyl ether, aliphatic alcohol polyoxyethylene, oleic acid diethyl amide etc., auxiliary component mainly play dispersion, stable or hydrotropy effect.When this auxiliary agent was water-soluble, the content of metallic compound was 30～80% (weight), and the content of solvent is 10～40% (weight), the content of auxiliary component is 10～30% (weight), and this moment, the cost of auxiliary agent was low, easy to use, be easy to clean, help labour protection; And when auxiliary agent was oil soluble, the content of metallic compound was 50～85% (weight), and the content of solvent is 10～30% (weight), the content of auxiliary component is 5～20% (weight), this moment auxiliary agent the cost height, toxicity is big, but dissolve each other with catalytically cracked material, dispersing property is good.
The using method of liquid sulfur transferring assistant provided by the invention, it is characterized in that it can be injected in the reactor with catalytic cracking charging or water vapor, also can be injected in reactor or the revivifier separately, loading system need not complex apparatus, only needs a basin, pump and respective lines to get final product.Sulfur transferring assistant can use separately, also can use with other fluid catalytic cracking auxiliary agent or logistics, as mix the back injecting reactor with metal passivator or slurry oil Scale inhibitors or riser reactor quenching oil.Here said catalytic cracking charging is meant fresh feed and/or recycle feed, i.e. recycle stock and reprocessed oil slurry.
The filling rate of liquid sulfur transferring assistant provided by the invention is not The more the better, if deposit sulfur transferring assistant on the catalyzer too much, metallic element in the auxiliary agent can influence activity of such catalysts and selectivity, in general, the deposition of sulfur transferring assistant is 0～3% (weight) on the catalyzer, be preferably in 2000～10000 μ g/g scopes, its filling speed depends on treatment capacity, feed sulphur content, the flue gas SO of catalytic cracking unit xThe multiple factors such as content of emission request and the effective ingredient of auxiliary agent own can also can be stopped using at any time according to the practical situation flexible.
The laboratory typical case preparation method of liquid sulfur transferring assistant provided by the invention is as follows: a certain amount of metallic compound is joined in the round-bottomed flask that has prolong, the organic acid or the mineral acid that add equivalent simultaneously, and the adding proper amount of solvent, under constantly stirring, reflux 3～15 hours, preferably 5～10 hours, raise the temperature to 100 ℃～130 ℃, be cooled to 50 ℃～80 ℃ then, add an amount of auxiliary component again, stirred 1～2 hour, and can obtain the uniform liquid product.
Liquid sulfur transferring assistant provided by the invention and using method thereof are applicable to the various device patterns of fluid catalytic cracking, comprise the catalytic cracking (FCC) of fraction oil, residual oil catalytic cracking (RFCC), deep catalytic cracking (DCC, claim catalytic pyrolysis again), and other utilizes fluid catalytic cracking successive reaction-regeneration principle to carry out the technological process of hydro carbons catalyzed conversion, as catalytic cracking family technical matters processes such as MGG, ARGG, MIO.
Liquid sulfur transferring assistant provided by the invention can make the SO in the regenerated flue gas xConcentration reduces by 40～80%, makes the sulphur content in the light-end products reduce by 5～30% simultaneously, and the activity and the selectivity of catalytic cracking catalyst in the system had no adverse effects.Because this sulfur transferring assistant is a liquid, so do not need the processing unit of complexity such as spraying drying in the preparation process, price is lower.The using method of liquid sulfur transferring assistant provided by the invention makes the filling rate of liquid sulfur transferring assistant be easy to flexible, and operation easily is automated control.
The sulphur transfer performance of liquid sulfur transferring assistant provided by the invention is estimated on fixed bed device.At first on reactor, pack into catalyzer 5 grams of sulfur transferring assistant dipping and burin-in process, under 730 ℃ of temperature, use reaction gas SO then 2, N 2, O 2Adsorbed 1 hour, and used N again 2Stripping 10 minutes is used reducing gas H at last 2, H 2O takes off SO at 520 ℃ of following desorptions xRate can be calculated as follows:
Figure A9812218700061
Further specify liquid sulfur transferring assistant provided by the invention and using method and effect by the following examples.
Embodiment 1
Claim 22.9 grams commercially available Phosbloc (purity＞99%), 8.4 gram magnesiumcarbonate (purity＞99%), 6.7 gram tin protoxides, 86.3 gram isocaprylic acids, No. 200 solvent oils of 10 grams and 0.5 gram hydroxybenzene polyoxydivinyl ether join in the round-bottomed flask that has prolong together.Under constantly stirring, be warmed up to 103～110 ℃, reacted 3 hours, be cooled to 80 ℃ then, add the commercially available triisobutyl aluminium of 9.7 grams, mix.Product is the dark-brown uniform liquid, and its character sees Table 1.
Embodiment 2
Claim 23 grams commercially available cerous carbonate (purity＞99%), 8.4 gram magnesiumcarbonate (purity＞99%), 11.6 restrain bismuthous oxide bismuth trioxides, 4.1 gram zinc oxide, 55.5 gram propionic acid and 10 gram water add in the there-necked flask that has the prolong backflow simultaneously.Add 8 gram dimethyl formamides under constantly stirring according to this, 3 gram glycol ethers are warmed up to 100～105 ℃ then, react 8 hours, are cooled to 50 ℃ then, add 3 gram ethyl formates, mix.Product is pale brown look uniform liquid, and its character sees Table 1.
The main physical and chemical of table 1 liquid sulfur transferring assistant
Project Embodiment 1 Embodiment 2
Physical condition The dark-brown uniform liquid Pale brown look uniform liquid
Density, 20 ℃, kg/m 3 ????1260 ????1530
Viscosity, 40 ℃, mm 2/s ????98 ????38
Solvability Oil is solvable Water soluble
Tenor m% lanthanum cerium magnesium bismuth Tin-zinc-aluminium ? ????10.8 ???? ????1.90 ???? ???? ????4.6 ????1.0 ? ???? ????10.9 ????1.9 ????83 ???? ????2.6 ????
Embodiment 3
Choose A, B, four kinds of catalyzer of C, D, wherein A, B are live catalyst, and C, D are industrial equilibrium catalyst, and its character sees Table 2.At first make catalyst A, B, C, D 450 ℃ of following roastings 2 hours, then use the liquid sulfur transferring assistant impregnated catalyst A of embodiment 1 preparation, liquid sulfur transferring assistant impregnated catalyst B, C, D with embodiment 2 preparations, respectively under 760 ℃, the condition of 100% water vapor aging 6 hours then, survey its micro-activity with huge port diesel oil (237～337 ℃) on micro-reactor, data rows is in table 3.As can be seen, prepared liquid sulfur transferring assistant has no adverse effects to catalyst activity, and tool is improved to some extent.After live catalyst and balance activity of such catalysts compared, as can be seen, the liquid sulfur transferring assistant was bigger to the active raising of live catalyst.
The main physico-chemical property data of table 2 catalyzer
Catalyzer ????A ????B ????C ????D
Chemical constitution % ?Al 2O 3 ????41.96 ????50.4 ????41.5 ????42.45
?Fe 2O 3 ????0.64 ????0.45 ????1.2 ????0.59
?Na 2O ????0.38 ????0.17 ????0.3 ????0.49
?Re 2O 3 ????1.96 ????/ ????2.98 ????1.42
Size composition m% ＜20μm ????3.6 ????2.8 ????3.1 ????0.50
?20～40μm ????14.3 ????18.9 ????18.4 ????3.30
?40～80μm ????55.9 ????60.8 ????54.8 ????70.70
＞80μm ????26.2 ????17.5 ????23.7 ????25.50
Physical properties Surface-area, m 2/g ????189 ????190 ????107 ????106
Pore volume, ml/g ????0.152 ????0.34 ????0.26 ????0.125
Tap density, g/cm 3 ????0.72 ????0.76 ????/ ????/
Lattice constant, A ????24.39 ????/ ????24.42 ????/
Micro-activity (760 ℃, 6h) ????70.5 ????67.0 ????60 ????61.7
Metal content μ g/g ????Ni ????/ ????/ ????4400 ????5800
????V ????/ ????/ ????520 ????1050
????Fe ????/ ????/ ????3600 ????4050
????Na ????/ ????/ ????4600 ????6100
Table 3 catalyst activity evaluation test result
The effective sulfur transferring assistant carrying capacity of catalyzer, μ g/g The catalyzer micro-activity, m%
????M * Catalyst A Catalyst B Catalyzer C Catalyzer D
????0 ????2000 ????4000 ????8000 ????12000 ????15000 ????70.1 ????70.8 ????70.5 ????71.4 ????72.6 ????73.0 ????67.0 ????67.2 ????67.8 ????68.4 ????68.9 ????70.1 ????60.2 ????59.8 ????60.0 ????61.4 ????61.9 ????62.2 ????61.7 ????61.5 ????61.8 ????62.5 ????63.1 ????62.8
*M: Ce: Mg: Bi: Zn: Al=2: 2: 1: 1: 1 (mol ratio)
Embodiment 4
Select catalyst sample A, C, the D of embodiment 3 preparations for use, investigate its sulphur and shift and regenerability.For this reason, on fixed-bed reactor, use reaction gas (SO respectively 20.12% (volume), O 23.5% (volume), N 296.38% (volume)) and reducing gas (H 298% (volume), H 2O 2% (volume)) adsorb, the desorption round-robin test, gas flow is 30 ml/min.At first adsorbed 1 hour with reaction gas, use N then at 730 ℃ 2Stripping 10 minutes uses reducing gas at 520 ℃ of following desorptions again, carries out this process repeatedly, measures the sulphur transfer effect.Test-results tabulation 4.
Table 4 liquid sulfur transferring assistant sulphur shifts test effect
The effective sulfur transferring assistant carrying capacity of catalyzer Take off SO xRate (v%)
Catalyst A Catalyzer C Catalyzer D
????M＝0????????????μg/g ????0 ????0 ????0
????M＝2000?????????μg/g ????38.1 ????45.5 ????43.7
????M＝4000?????????μg/g ????45.0 ????49.7 ????51.6
????M＝6000?????????μg/g ????48.8 ????54.6 ????57.3
????M＝8000?????????μg/g ????53.3 ????60.5 ????62.4
????M＝10000????????μg/g ????63.8 ????70.9 ????74.1
Embodiment 5
Use the liquid sulfur transferring assistant and the catalyzer C of embodiment 1 preparation, be to adopt using method provided by the invention on the FCC riser tube pilot plant test device of 4kg at catalyst inventory, with ram pump the liquid sulfur transferring assistant is injected in the used Central Plains mixing long residuum (its character sees Table 5) of test, and enters reactor together.Under the listed test conditions of table 6, investigate the result of use of this liquid sulfur transferring assistant, with SO in the flue gas xRepresent its sulphur transfer efficiency with the percentage ratio that the blank contrast is reduced.
Table 7 is listed in the sulfur distribution situation in the FCC cracked product when adopting different liqs sulfur transferring assistant filling rate in the stock oil, table 8 is listed in the stock oil when adopting different liqs sulfur transferring assistant filling rate the distribution situation of mercaptan sulfur and thiophenic sulfur in the FCC pressure gasoline, as can be seen, be deposited on sulfur transferring assistant total metal content on the catalyzer when being 5000～12000ppm, SO in the regenerated flue gas xQuantity discharged has reduced by 40～80%, and sulphur content has reduced by 5～30% in the lightweight oil.
Table 5 stock oil character
Project Data
Density, 20 ℃, kg/m 3 ????910.2
Molecular weight ????454
Carbon residue, m% ????5.68
Viscosity, mm 2/s ??80℃ ????89.5
??100℃ ????15.6
Ultimate analysis, the hydrocarbon sulphur nitrogen of m% ? ????86.49 ????12.60 ????0.7384 ????0.1628
Group composition, m% stable hydrocarbon aromatic hydrocarbons colloid+bituminous matter ? ????52.6 ????33.4 ????14.0
Boiling range, ℃ 10% 30% 60% 90% ? ????319 ????413 ????508 ????678
Table 6 riser tube FCC medium-sized test condition
The riser tube temperature out, ℃ ????520
The feeding preheating temperature, ℃ ????340
Regenerator temperature, ℃ ????720
Reactor pressure, MPa ????0.15
Reaction times, s ????2.9
Agent-oil ratio ????7.0
The atomizing water yield, m% ????6.5
The distribution (m%) of table 7 raw material sulphur in the FCC product
Catalyzer C *μg/g Gasoline Solar oil Slurry oil Reacted gas Coke Flue gas
??M＝0 ????5.43 ????13.28 ????10.27 ????56.08 ????14.62 ????14.62
??M＝5000 ????5.18 ????13.16 ????10.62 ????56.32 ????14.72 ?????8.79
??M＝8000 ????4.69 ????12.84 ????10.96 ????56.66 ????14.85 ?????7.43
??M＝12000 ????3.80 ????12.49 ????11.20 ????57.35 ????15.16 ?????2.92
Annotate: *M Ce: Mg: Bi: Zn: Al=2: 2: 1: 1: 1 (mol ratio)
The distribution (%) of raw material sulphur in the FCC product meets following formula:
Gasoline %+ solar oil %+ slurry oil %+ reacted gas %+ flue gas %
=gasoline %+ solar oil %+ slurry oil %+ coke %+ reacted gas %-(coke %-flue gas %)=100%
The variation of mercaptan sulfur and thiophenic sulfur in the table 8 FCC pressure gasoline
Catalyzer C *μg/g ????M＝0 ????M＝5000 ????M＝8000 ????M＝12000
Mercaptan sulfur (m%) ????0.23 ????0.16 ????0.08 ????0.17
Thiophenic sulfur (m%) ????5.20 ????5.02 ????4.57 ????3.99
*M Ce: Mg: Bi: Zn: Al=2: 2: 1: 1: 1 (mol ratio)

Claims (8)

1. sulfur transferring assistant for catalytic cracking of hydrocarbon, be by metallic compound, oil soluble or water miscible molecule or colloidal solution that solvent and auxiliary component are formed, emulsion or suspension, wherein metallic compound is the oxide compound of metal, oxyhydroxide, organic acid salt, inorganic acid salt or its complex compound, described metal is an alkaline-earth metal, in three groups of metals of transition metal and rare earth metal two or more, and it is selected from least two group metals, solvent is a water, alcohols or hydro carbons, auxiliary component is an alcohols, ethers, the ester class, amine, amides, alcamines or ionic, nonionic surface active agent, when auxiliary agent when being water-soluble, the content of metallic compound is 30～80% (weight), the content of solvent is 10～40% (weight), and the content of auxiliary component is 10～30% (weight); When auxiliary agent was oil soluble, the content of metallic compound was 50～85% (weight), and the content of solvent is 10～30% (weight), and the content of auxiliary component is 5～20% (weight).
2. sulfur transferring assistant for catalytic cracking of hydrocarbon according to claim 1, wherein metallic compound is the organic acid salt of metal, the used organic acid of organic acid salt is selected from one or more in saturated carboxylic acid, unsaturated carboxylic acid, substituted carboxylic acid and the Phenylsulfonic acid.
3. sulfur transferring assistant for catalytic cracking of hydrocarbon according to claim 1, wherein metallic compound is the inorganic acid salt of metal, the used mineral acid of inorganic acid salt is selected from nitric acid, phosphoric acid and sulfonic acid.
4. sulfur transferring assistant for catalytic cracking of hydrocarbon according to claim 1, wherein said catalytic cracking are meant that the catalytic cracking of fraction oil, residual oil catalytic cracking, deep catalytic cracking and other utilize fluid catalytic cracking reaction-regeneration principle to carry out the technological process of hydro carbons catalyzed conversion.
5. the using method of the described sulfur transferring assistant for catalytic cracking of hydrocarbon of claim 1, when sulfur transferring assistant uses, can be injected in the reactor with catalytic cracking charging or water vapor, also can be injected into separately in reactor or the revivifier, its deposition on catalyzer is 0～3% (weight).
6. the using method of sulfur transferring assistant for catalytic cracking of hydrocarbon according to claim 5, wherein the deposition of sulfur transferring assistant on catalyzer is 2000～10000 μ g/g.
7. the using method of sulfur transferring assistant for catalytic cracking of hydrocarbon according to claim 5, wherein the catalytic cracking charging is meant fresh feed and/or turning oil charging.
8. according to the using method of claim 5 or 6 or 7 described sulfur transferring assistant for catalytic cracking of hydrocarbon, wherein sulfur transferring assistant can use with other liquid assistant for calalytic cracking or logistics, also can use separately.
CN98122187.4A 1998-12-29 1998-12-29 Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage Expired - Fee Related CN1122702C (en)

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US10/292,681 US6790343B2 (en) 1998-12-29 2002-11-12 Sulfur transfer additive for catalytic cracking of hydrocarbons and a catalytic cracking process of hydrocarbons using the same

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